[Pd(μ-Br)(P(t)Bu3)]2 as a highly active isomerization catalyst: synthesis of enol esters from allylic esters.

The dimeric Pd(I)-complex [Pd(μ-Br)(P(t)Bu3)]2 was found to be highly active for catalyzing double-bond migration in various substrates such as unsaturated ethers, alcohols, amides, and arenes, under mild conditions. It efficiently mediates the conversion of allylic esters into enol esters, rather than inserting into the allylic C-O bond. The broad applicability of this reaction was demonstrated with the synthesis of 22 functionalized enol esters.